ES2197510T3 - USE OF IMPROVED INTERNAL DISMOLDING AGENTS TO MANUFACTURE BODIES OF POLISHED MOLDING REINFORCED WITH GLASS FIBERS AND / OR NATURAL FIBERS. - Google Patents

Abstract

Use of internal mold release agents for the manufacture of polyurethane molding bodies, reinforced with glass fibers and / or natural fibers, the mold release agents being composed of a) ammonium or metal salts of phosphoric acid esters of formula (I) ** FORMULA ** in which R represents C1-C10 alkyl, X means OR1, with R1 equal to R or O-Y + and Y represents NH4 and N (R2, R3, R4, R5), in which R2 to R5 they are the same or different, and mean hydrogen or C1-C10 alkyl, the C1-C10 alkyl moiety may be substituted, once or several times, by OR6 or NR6R7 and R6 and R7 have the meaning of hydrogen or C1-C10 alkyl, or in which R2 to R5 means ** FORMULA ** in which R8 and R9 are the same or different and represent C1-C10 alkyl or hydrogen and m means an integer from 2 to 4 and n an integer from 1 to 5, and in the that at least one of the radicals R2, R3, R4 or R5 means hydrogen, or Y represents metals of the first major group of the periodic system or of the elements (Mendelejew), and, if necessary, in admixture with b) ammonium salts of carboxylic acids, of formula (II) R10COO-Z + (II), in which R10 represents hydrogen, C1-C9 alkyl or aryl C6-C10, which, optionally, may be substituted by C1-C3 alkyl groups, and Z has the meaning of Y, with the exception of the mentioned metals, of the first major group of the periodic system of the elements, and / or, given the case, c) ammonium or metal salts of sulfonic acids of formula (III) ** FORMULA ** in which R11 has the meaning of R16 and Y has the meaning indicated in formula (I).

Description

Use of improved internal mold release agents for manufacturing fiber reinforced polyurethane molding bodies of glass and / or natural fibers.

The present invention concerns the use of internal demolding to manufacture polyurethane molding bodies, cellular or compact, reinforced with glass fibers and / or fibers natural, especially those that are lined or coated by other materials.

Internal mold release agents for manufacture of polyurethane molding bodies, especially Polyurethane foams have been known for a long time. So by example, in documents DE-A 2121670, 1953637 and 2307589 mold release agents are described in the manufacture of foams, which are composed of salts of carboxylic acids aliphatic with, preferably, primary amines or amines that they contain amide or ester groups, whose total number of atoms of Carbon amounts to at least 25 carbon atoms.

In US 4024088, among others, they mention organophosphorus compounds, such as mold release agents internal, which, at least, contain 8 carbon atoms in the molecule. In addition, from US 4098731 agents of internal mold release, based on metal salts of an acid carboxylic acid, an amidocarboxylic acid, phosphoric acid or acid boric, in combination with certain tertiary amines. The US 4098731 also describes internal mold release agents in the manufacture of polyurethane molding bodies, based on salts of carboxylic acids, with at least 8 atoms of carbon and tertiary amines. In addition, from US 4220727 it they know internal mold release agents, which, among others, are composed of metal salts of fatty acids and certain quaternary salts of aralkylammonium. Zinc carboxylates with long chain carboxylic moieties (8 to 24 carbon atoms) are known as internal mold release agents, for example, of the US 4519965, US 4581386 and US 4111861. In addition, the use of higher esters of fatty acids, as mold release agents is known from US4130698.

The release agents, known so far, they have the most diverse disadvantages in the manufacture of bodies of molding of cellulose or compact polyurethane. So, the salts metallic of higher carboxylic acids, after some time, they tend to crystallize and gel formation, when adds them to the starting components for the manufacture of polyurethane molding bodies, so they are altered unfavorably the viscosity and rheological behavior of Polyurethane masses. In the case of other mold release agents, especially those with non-polar or polar components by the often insufficient solubility of the components in the starting substances of polyurethane, a system is formed biphasic, which leads to processing difficulties in moldable polyurethane materials.

Another major disadvantage of mold release agents known interns so far is the so-called accumulation in the mold, by which, after longer cycles, gradually it mold contours deteriorate. Fine contours, glued and added polyurethane dough from used molds, they can only be returned to the original state through expensive subsequent cleaning, which, of course, forces a production interruption

Therefore, it is the objective of the present invention provide internal mold release agents that prevent disadvantages of current demoulding, described above and, therefore, in general, present an improved picture of properties.

Therefore, the object of the present invention is the use of improved internal mold release agents for manufacturing of glass fiber reinforced polyurethane molding bodies and / or natural fibers, composed of

a) Ammonium or metal salts of acid esters phosphoric of formula (I)

one

in the what

R

represents alkyl C 1 -C 10, preferably alkyl C_ {4} -C_ {8},

X

 means OR1, with R 1 equal to R or O - Y + e

Y

represents NH4 and N (R 2, R 3, R 4, R 5), wherein R 2 a R5 are the same or different and mean hydrogen or alkyl C_ {1} -C_ {10}, and the C 1 -C 10 alkyl moiety, once or several times, by OR 6 or NR 6 R 7, and R 6 and R 7 possess the meaning of hydrogen or alkyl C 1 {C 10},

or in which R 2 to R 5 mean

two

in the what

R 8 and R 9 are the same or different and represent C 1 -C 10 alkyl or hydrogen,

m means an integer from 2 to 4 and

n an integer from 1 to 5,

and in which at least one of the remains R 2, R 3, R 4 or R 5 means hydrogen,

or

And represents metals of the first main group of the periodic system of the elements (Mendelejew),

and, if necessary, mixed with

b) ammonium salts of carboxylic acids of formula (II)

R 10 COO - Z + qu (II), in which

R 10

It represents hydrogen, C 1 -C 9 alkyl or aryl C_ {6} -C_ {10} which, optionally, can be substituted by C 1 -C 3 alkyl groups, Y

Z

it has the meaning of Y, with the exception of the mentioned metals of the first group principal of the periodic system of elements,

and / or, given the case,

c) ammonium or metal salts of acids sulfonic acids of formula (III)

3

in the what

R 11 has the meaning of R 10 and Y It has the meaning indicated in formula (I).

As alkyl residues C_ {1} -C_ {10} of the aforementioned formulas above, especially they are mentioned:

n-butyl, iso-butyl, n- and iso-pentyl, 2-ethylhexyl, octyl, n-propyl, iso-propyl, ethyl, methyl, nonyl, decyl, especially n- and iso-butyl, n- e iso-pentyl, 2-ethylhexyl, octyl.

The rest Y, of the formula above mentioned, preferably, represents NH4 +,

4

5

Preferably, m represents an integer of 2 to 3 and n from 1 to 3.

As metals of the first major group of periodic system of the elements, especially, can be Mention: lithium, sodium, potassium.

As mold release agents for the manufacture of Polyurethane molding bodies, the following salts are especially appropriate:

6

61

7

The following salts are very especially preferred:

8

9

As mentioned, the release agents according to the invention they are suitable for manufacturing molding bodies of polyurethane, cellular and compact.

Polyurethane molding bodies can be manufacture as usual by reaction of

to)

 polyisocyanates or polyisocyanate prepolymers with

b)

 at least one compound that has at least two reactive groups against isocyanates, with a molecular weight of 400 to 10,000, if necessary, in the presence of chain extenders, of molecular weight 32 to 399, being able to carry out the reaction of components a) and b), given the case, in the presence of water and / or organic expansion agents, stabilizers, activators, as well as other adjuvants and additives known.

In addition to additives, previously mentioned, to the polyurethane masses obtained in the processing, loading materials can be added organic as well as inorganic to reinforce the molding bodies. Name, for example, glass fibers, wollastonite, sisal, linen, Jute, hemp and / or wood chip.

As stabilizers, first of all, they enter Consideration polyethersiloxanes. These compounds, in general, are compounds in this way: a short chain oxide copolymer of ethylene and propylene oxide, is linked with a residue polydimethylsiloxane. Such foam stabilizers, for example, are described in US-PS 2834748, 2917480 and 3629308, as well as US-PS 2917480.

As catalysts, for example, you can state: tertiary amines, such as triethylamine, tributylamine, N-methylmorpholine, N-ethylmorpholine, N, N, N ', N'-tetramethyl-ethylenediamine, pentamethyl diethylenetriamine and higher homologues (documents DE-A 2624527 and 2624528), 1,4-diazabicyclo- (2,2,2) -octane, N-methyl-N'-dimethylaminoethylpiperazine, bis- (dimethylaminoalkyl) -piperazine, N, N-dimethylbenzylamine, N, N-dimethylcyclohexylamine, N, N-diethylbenzylamine, adipate bis- (N, N-diethylaminoethyl, N, N, N ', N'-tetramethyl-1,3-butanediimine, N, N-dimethyl-? -Phenylethylamine, 1,2-dimethylimidazole, 2-methylimidazole, monocyclic amidines and bicyclic as well as ethers bis (dialkylamino) alkyl, such as ether 2,2-bis- (dimethylaminoethyl), but also metal carboxylates, such as potassium acetate or octoate potassium.

As catalysts can also be used organic metal compounds, especially organic compounds tin. As organic tin compounds, in addition to sulfur-containing compounds, such as mercaptide of di-n-octyltin preferably tin (II) salts of acids come into consideration carboxylic, such as tin (II) acetate, octoate tin (II), tin ethylhexoate (II) and laurate tin (II), and tin compounds (IV), by example, dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin dilaurate, maleate dibutyltin or dioctyltin diacetate.

To obtain, for example, molding bodies of Cellular polyurethane, the reaction of the component a) with component b) as mentioned, with water and / or organic expansion agents. As organic expansion agents, all known expansion agents come into consideration, especially hydrocarbons, such as n-pentane, c-pentane and isopentane, as well as hydrocarbons fluorinated such as tetrafluoroethane and monofluorichloroethane.

As polyisocyanates or prepolymers of polyisocyanate (component a), the aliphatic, cycloaliphatic, araliphatic isocyanates, preferably aromatic, polyfunctional known, as, by example, they are mentioned in document EP-A 364858. Especially appropriate are Toluylene diisocyanates and diphenylmethane diisocyanates, their products modified or their corresponding prepolymers, which may be modified by urethane, urea, biuret, allophanate groups, carbodiimide or uretdione. Especially, they are mentioned as aromatic polyisocyanates: 4,4'-diphenylmethanediisocyanate, mixtures of 2,4'- and 4,4'-diphenylmethanediisocyanate or types of raw methyldiisocyanates.

As reaction component b), especially, polyols or mixtures of polyols, which have a OH index from 20 to 1800, adjusting an average OH index of 300 to 900 in total. The individual components b) have a weight Average molecular from 400 to 10,000.

They proved especially convenient polyether polyols and polyester polyols, which are obtained by adding an alkylene oxide, such as ethylene oxide or propylene oxide, to polyfunctional initiators, such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane, sorbitol, ethylenediamine or by condensation of dicarboxylic acids, such as adipic acid, acid succinic, glutaric acid, subic acid, sebacic acid, acid maleic, phthalic acid, with predominantly hydroxycomponents bifunctional, such as ethylene glycol, propylene glycol and diethylene glycol

As chain extenders that can be added in the reaction together with component b), especially, compounds with molecular weights of 32 are suitable to 399. Mentioned: ethylene glycol, 1,4-butanediol, glycerin, trimethylolpropane adducts, glycerin, pentaerythrite, sorbitol, with propylene oxide and / or ethylene oxide.

The release agents according to the invention, they are usually used in amounts of 0.5 to 20, preferably 1 to 15 parts by weight, based on 100 parts by weight of the component reagent b).

With the help of internal mold release agents according to the invention, for example, bodies of molding of polyurethane, cellular, by the procedure of Foaming molding, working in closed molds, with foaming a reaction mixture of polyisocyanates, compounds with atoms of hydrogen reagents, water and / or organic blowing agents and, given the case, other adjuvants and additives, using additionally internal mold release agents, mentioned above, to mold temperatures of preferably 60-75 ° C approximately. The manufacture of polyurethane molding bodies, for example, it is described in Kunststoffhandbuch (Manual of plastics), volume 7, Polyurethane, 3 revised edition, Carl Editorial Hanser, Munich / Vienna, 1993.

PUR molding bodies manufacturing corresponding, reinforced by natural fiber mats or fiberglass, from exempt PUR reaction mixtures or almost free of foaming agents, it is done by compression molding process at mold temperatures of approximately 95 to 135 ° C.

As already mentioned, the release agents according to the invention they generate an excellent separation capacity, a good rheological and impregnation behavior in the components used a) and b), for the manufacture of polyurethane doughs and they do not tend to accumulate in the mold, that is, a soiling of the mold by polyurethane masses that deposit.

Examples Description of raw materials I) Mold components according to the invention (TK)

one.

10

From 210 g (1 mol) of dibutyl phosphate by drip addition of 145 g (1 mol) of 3-dimethylaminopropylurea, at 30 ° C.

Acid Index: 158 mg of KOH / g

P.F .: 105 ° C

two.

eleven

From 210 g (1 mol) of dibutyl phosphate by drip addition of 130 g (1 mol) of 3-dimethylaminopropylformamide at 30 ° C.

Acid index: 165 mg of KOH / g

P.F .: 35ºC

3.

HOC 2 H 4 -N (CH 3) 2 H + (C 4 H 9 O) 2 PO 2 -

From 210 g (1 mol) of dibutyl phosphate by drip addition of 89 g (1 mol) of N, N-dimethylethanolamine.

Acid Index: 187 KOH / g

Four.

HOC 2 H 4 -N (CH 3) 2 H + (C 8 H 17 O) 2 PO 2 -

From 322 g (1 mol) of phosphate bis-2-ethylhexyl by addition by drip of 89 g (1 mol) of N, N-dimethylethanolamine.

Acid Index: 135 mg of KOH / g

5.

HOCH 2 CH 2 N (CH 3) 2 H + C 7 H 15 -COO -

From 144 g (1 mol) of acid 2-ethylhexanoic and 89 g (1 mol) of N, N-dimethylethanolamine.

Acid index: 240 mg of KOH / g

6.

HOCH 2 CH 2 N (CH 3) 2 H + CH 3 C 6 H 4 -SO 3 {-}

From 172 g (1 mol) of acid 3-methylbenzenesulfonic acid and 89 g (1 mol) of N, N-dimethylethanolamine.

Acid Index: 213 mg of KOH / g

II) Polyols

Polyol one

Polyether polyol, with OH index 470, manufactured by adding propylene oxide to a starter mixture of 80 parts by weight of sugar, 15 parts by weight of propylene glycol and 5 parts by weight of water.

Polyol two

Polyether polyol, with OH index 380, manufactured by adding propylene oxide to a starter mixture of 45 parts by weight of sugar, 50 parts by weight of diethylene glycol, 5 parts by weight of water.

Polyol 3

Polyether polyol, with OH index 865, manufactured by the addition of propylene oxide to trimethylolpropane

Polyol 4

Polyether polyol, with OH index 515, manufactured by the addition of propylene oxide to propylene glycol.

Polyol 5

Polyether polyol, with OH index 475, manufactured by adding propylene oxide to a 80% sugar and 20% propylene glycol starter mixture.

Polyol 6

Polyether polyol, with OH index 1000, manufactured by the addition of propylene oxide to trimethylolpropane

Polyol 7

Polyether polyol, with OH index 640, manufactured by adding propylene oxide to ethylenediamine as initiator.

Polyol 8

Polyether polyol, with OH index 480, manufactured by adding propylene oxide to ethylenediamine, as initiator.

Polyol 9

Polyether polyol, with OH index 42, manufactured by adding 86% propylene oxide and 14% from ethylene oxide to propylene glycol, as initiator.

III Polyisocyanates

Polyisocyanate, manufactured by reaction of fatty acid polyester C of DE-OS 2307589, to give a prepolymer according to example 1, of the document DE-OS 2307589, with an NCO content of 28.4%.

Examples of realization

The reaction components were used to manufacture lining parts and drawings of plates, wall thin. Manufacturing was carried out under the usual conditions of PUR processing.

Raw material temperatures, during the processing was between 25 and 30 ° C.

Formulation 1

       \ dotable {\ tabskip6pt # \ hfil \ + \ hfil # \ tabskip0ptplus1fil \ dddarstrut \ cr} {
 Polyol 1 \ 40 \ parts 40 by weight \ Polyol 2
50 parts by weight \ Polyol 3 \ quad \ + \ 10
parts by weight \ TK component 1 \ + 10 parts in
Weight \ Dilaurate of \ + \ 0.15 parts by weight \ cr
Dibutyltin (DBTDL) \ + \ cr K acetate \ + \ 0.5 parts
by weight \ cr (25% in SDR) \ + \ cr Polyisocyanate 1 \ + \ quad
129 parts in
weight \ cr}
    

Approximately 250 g of the formulation, on both sides of a natural fiber mat of sisal / linen (1: 1), weight per area of 1000 g / m2, and then it was compressed in a steel mold with an area of approximately 1 m 2, at a temperature of 125-135 ° C, for 60-80 s, for get a wall thickness of 1.8-2 mm.

After opening the mold, the molded part, without demoulding aids. They were made more than 250 demouldings, without visible deposits of mass in the mold, there was a separation in the first release.

Formulation 2

Analogous to formulation 1, instead of TK 1, it they used 10 parts by weight of the TK 2 component and it was processed so correspondent.

The molded part left the mold without problem, at the first demoulding, no deposit of substance in the mold, after the prolonged course of the production.

Formulation 3

Analogous to formulation 1, instead of TK 1, it dissolved 8 parts by weight of the TK 3 component, and processed corresponding way.

The lining piece left the mold without problems, no substance deposit could be found in the mold, even after a long period of operation.

Formulation 4

Analogous to formulation 1, instead of TK 1, it They used 8 parts by weight of the TK 4 component.

The molded part separated somewhat more unfavorably of the mold, which with formulation 3, could not verify any deposit, after prolonged operation of the production.

Formulation 5

Analogous to formulation 1, instead of TK 1, it They used 10 parts by weight of the TK 5 component.

The door liner left the mold without problems, from the beginning, it was not possible to verify any deposit, after a prolonged duration of manufacture.

Formulation 6

Analogous to formulation 1, instead of TK 1, it They used 10 parts by weight of the TK 6 component.

The door liner left the mold without problems, no deposit could be found in the mold, after prolonged operation.

The good processing properties of formulation variants, set forth above, were emphasized due to the fact that in molds with conditioned partial accumulation by the use of formulations based on agent compositions of conventional internal demoulding, immediately, got a good effect of separation and the deposit disappeared in the subsequent course of manufacturing.

In addition, the adhesion without problems of fixing elements and plastic inserts. These were placed in the mold, and during compression molding, they joined with the PUR matrix. Start break tests proved good Adhesive results with a cohesive behavior of break.

All formulations were stable in the storage, at least, for 6 months, and without reducing the reactivity.

If in formulations 1 to 6 according to the document US-PS 4585803, example 3, as a mold release agent, 5 parts of zinc stearate, dissolved in 5 parts of Amine 5 as a solubilizer, a solution was first obtained transparent that, however, over the course of a week it clouded, gelled and strongly increased viscosity. It could be processed and applied on natural fiber mats used in a considerably worse way. They also saw each other negatively influenced rheological behavior or impregnation of natural fiber mats, in the process of compression.

Formulation 7

       \ dotable {\ tabskip6pt # \ hfil \ + \ hfil # \ tabskip0ptplus1fil \ dddarstrut \ cr} {
 Polyol 3 + 30 parts by weight \ Polyol 6
20 parts by weight \ Polyol 9 \ quad \ + \ quad
33.5 parts by weight \ Polyurax SR 242 (OSi company) \ quad \ + \ quad
2.3 parts by weight \ cr Thancat AN 10 (Air \\ \ company 1.3
parts by weight \ cr Products) \ + \ cr Acetic acid \ quad \ + \ quad
0.3 parts by weight \ Cr Water \ + \ 1.4 parts in
Weight \ cr Baydur Schwarzpaste DN \ 3.3 \ parts
Weight \ cr (Bayer AG company) \ + \ cr Component TK 4 \ + \ quad
8 parts by weight? Polyisocyanate 1 \ 154 \ parts
weight \ cr}
    

The formulation was introduced in a steel mold 600 x 1000 x 3 mm in size, which contained a glass mat of weight per surface area of 600 g / m2, as a supplementary piece, in the usual conditions for the processing of raw materials of polyurethane. The mold temperature amounted to approximately 75 ° C A total apparent density of 950 kg / m3 was found. The demolding time amounted to 120 s.

The molded parts could be removed without problems with the first part, of the open mold, without produced a product deposit in the mold, after numbers older than demolding.

Formulation 8

Analog formulation at 7, changing the component TK 4 per 8 parts by weight of component TK 1, dissolved by heating.

The plate fell out of the mold when it opened. I dont know observed an accumulation in the mold of raw materials that will deposit gradually or even after manufacturing large number of pieces.

It was achieved without problems and without treatment costly after, parts after processing manufactured moldings, such as foaming of PUR foam systems semi-hard, cladding with films and decorative plates, based, for example, on ABS, PVC, TPO and textile materials multilaminar, as well as bonding with adhesives PUR-2C appropriate.

Through the procedure they can be manufactured external and internal parts of automobiles as linings of doors, seats as well as trays, column coverings A, B and C, rear trays, luggage racks, chassis sunroof, dashboard brackets and enclosure closures motor.

Claims (1)

1. Use of internal mold release agents for manufacture of polyurethane molding bodies, reinforced with glass fibers and / or natural fibers, the compounds being composed mold release agents a) Ammonium or metal salts of acid esters phosphoric of formula (I) 12 in the what

R

represents alkyl C 1 {C 10},

X

means OR1, with R 1 equal to R or O - Y + e

Y

represents NH4 and N (R 2, R 3, R 4, R 5), wherein R 2 a R5 are the same or different, and mean hydrogen or alkyl C_ {1} -C_ {10}, and the C 1 -C 10 alkyl moiety, once or several times, by OR 6 or NR 6 R 7 and R 6 and R 7 possess the meaning of hydrogen or alkyl C 1 {C 10},

or in which R 2 to R 5 mean 13 in the what R 8 and R 9 are the same or different and represent C 1 -C 10 alkyl or hydrogen Y m means an integer from 2 to 4 and n an integer from 1 to 5, and in which at least one of the remains R 2, R 3, R 4 or R 5 means hydrogen, or And represents metals of the first main group of the periodic system of the elements (Mendelejew), and, if necessary, mixed with b) ammonium salts of carboxylic acids, of formula (II) R 10 COO - Z + \ (II),} in the what

R 10

 It represents hydrogen, C 1 -C 9 alkyl or C 6 aryl - C 10, which, optionally, may be substituted by groups C 1 -C 3 alkyl, and

Z

 owns the meaning of Y, with the exception of the metals mentioned, of first major group of the periodic system of the elements,

and / or, given the case, c) ammonium or metal salts of acids sulfonic acids of formula (III) 14 in the what R 11 has the meaning of R 10 and Y It has the meaning indicated in formula (I).